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Accident Creates Safe Perfect Blue Pigment

November 17, 2009

An accidental discovery in a lab at Oregon State Univ. has apparently solved a quest that over thousands of years has absorbed the energies of ancient Egyptians, the Han dynasty in China, Mayan cultures and more--the creation of a near-perfect blue pigment.


Through much of recorded human history, people around the world have sought inorganic compounds that could be used to paint things blue, often with limited success. Most had environmental or durability issues. Cobalt blue, developed in France in the early 1800s, can be carcinogenic. Prussian blue can release cyanide. Other blue pigments are not stable when exposed to heat or acidic conditions.

But chemists at OSU have discovered new compounds based on manganese that should address all of those concerns. They are safer to produce, much more durable, and should lead to more environmentally benign blue pigments than any being used now or in the past. They can survive at extraordinarily high temperatures and don’t fade after a week in an acid bath.

The findings were just published in the Journal of the American Chemical Society, and a patent has been applied for on the composition of the compound and the process used to create it.

“Basically, this was an accidental discovery,” says Mas Subramanian, Professor of Materials Science in OSU's Dept. of Chemistry. “We were exploring manganese oxides for some interesting electronic properties they have, something that can be both ferroelectric and ferromagnetic at the same time. Our work had nothing to do with looking for a pigment. Then one day a graduate student who is working in the project was taking samples out of a very hot furnace while I was walking by, and it was blue, a very beautiful blue. I realized immediately that something amazing had happened.”

What had happened, the researchers said, was that at about 1,200 C, this otherwise innocuous manganese oxide turned into a vivid blue compound that could be used to make a pigment able to resist heat and acid, be environmentally benign and cheap to produce from a readily available mineral.

The newest--and possibly the best--blue pigment in world history was born, due to manganese ions being structured in an unusual “trigonal bipyramidal coordination” in the presence of extreme heat.

“Ever since the early Egyptians developed some of the first blue pigments, the pigment industry has been struggling to address problems with safety, toxicity and durability,” says Subramanian.

The pigment may eventually find uses in everything from inkjet printers to automobiles, fine art or house paint, researchers say.

The scientists said in their journal article that the new compound yields “a surprisingly intense and bright blue color,” and they have outlined its structure and characteristics in detail. Collaborating on the work were researchers in the Materials Department at the University of California/Santa Barbara.

“A lot of the most interesting discoveries are not really planned, we’ve seen that throughout history,” says Subramanian. “There is luck involved, but I also teach my students that you have to stay alert to recognize something when it happens, even if it isn’t what you were looking for. Luck favors the alert mind.”

Source: Oregon State Univ.


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Comments
Enzo 12/29/2010 10:53:52 AM
I'm an oil paint artist and I use sometimes genuine Manganese blue (PB-33)in my paintings. I could make up an imitation hue by using Phthalocyanine blue(PB-15:4). In my research of the pigments the Old Masters used in the 1800's to the early 1900's ,I read that by heating Barium nitrate with Potassium permanganate at 800 degrees centigrade yields the standard manganese blue that we use . Would someone out there know of a way to produce this beautiful blue pigment without the application of heat ? A cold process ? Regards.

Pie 11/27/2010 8:51:20 PM
So is this manganese in the +5 oxidation state? I've heard its blue and very hard to produce at normal, room conditions.

Lisa 9/4/2010 2:13:42 PM
The patent office has no rule against accidental inventions being patented. As long as you realize what it was that caused the result (e.g., the blue pigment here) and can describe the process step by step, and you meet the other requirements for patentability, you can patent it. However, I don't know whether this particular discovery qualifies for a patent; it may just constitute a scientific discovery ("if you heat manganese oxide at 1200 degrees, it turns blue")--that is, a discovery of a property of nature--and those can't be patented. What could be patented, though, are useful applications for that discovery such as printers or processes for painting cars, etc., using this pigment.

Henry 8/17/2010 11:17:11 AM
There are several things wrong about these claims. I make art glass fusings at 1300 degrees F. At that color everything looks red. Also, the Patent Office in the US does not allow Accidents to be patented. Any Patent must show deliberate intent and purpose. This person just BS'ed themselves out of any commercial value. Brad S. is most likely correct.

Not-so-sure-this-is-new 4/8/2010 5:45:49 PM
This event does not sound unique or unusual as I currently have a piece of 4130 heat treated to 45HRc that has a brilliant blue surface, something I've seen a couple of hundred times. What makes the "new blue" better or new? Is that it will be easy to collect or use? Besides, every heat treater knows that you see color of the temperature, not material type or condition at temperature. Just as an experiment does your inconel sheathed type K thermocouple glow the same color or brilliance as the steel being heat treated around it? Mine does.....

Brad S 2/9/2010 7:05:38 PM
Regarding Subramanian's self-congratulation, his story sounds like a lie. He said he spotted the color when a grad student "was taking samples out of a very hot furnace while I was walking by, and it was blue, a very beautiful blue". This story reeks. I am a professional glassmaker and know that at "very high" temperatures virtually no colors look the same as at room temperature. While there are a few exceptions to that, this story as told sounds like so much bull. It seems far more likely that the grad student showed him the color after the piece had cooled. But if that was the case it would be a lot tougher for Subramanian to claim to be the "discoverer" of the pigment.

unclesmrgol 11/30/2009 7:46:49 PM
One wonders if the graduate student will ever forgive his professor for stealing his thunder. Having worked in academia, I've seen that the "stealing thunder" scenario is entirely possible -- especially given Subramanian's self-congratulation.

Tom Langley 11/21/2009 2:49:22 AM
I wonder if this pigment would have application in fireworks as the current copper based blue pigments are not heat stable. The current pigments don't have an adequate color for this reason.

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